Isomer-directed process for producing asymmetric ketones using catalytic Claisen rearrangement of allylic ethers, intermediates, and uses of products and intermediates of process in perfumery

ABSTRACT

Described is an isomer-directed process for producing asymmetric ketones defined according to the generic structure: ##STR1## wherein one of Z 1  or Z 2  is the moiety: ##STR2## and the other of Z 1  or Z 2  is hydrogen; wherein R 11  and R 21   represent hydrogen or the same or different alkyl or alkenyl with the proviso that R 11  and R 21  are not both hydrogen or wherein R 11  and R 21  taken together: 
     (i) complete a cycloalkyl, cycloalkenyl, bicycloalkyl, mono or polyalkyl cycloalkyl or mono or polyalkyl cycloalkenyl ring, or 
     (ii) represent alkylidene, cycloalkenyl alkylidene, aralkylidene, mono or polyalkyl cycloalkenyl alkylidene or mono or polyalkyl aralkylidene; 
     and wherein R 6 , R 7  and R 8  are the same or different and each represents hydrogen or methyl, using a catalytic Claisen rearrangement of allylic ethers previously formed by reacting substituted or unsubstituted allylic alcohols defined according to the structure: ##STR3## with dialkyl ketals defined according to the structure: ##STR4## wherein R 4  and R 5  represent the same or different C 1  -C 4  alkyl. 
     Also described are compounds and processes for using same in perfumery defined according the structures: ##STR5## Also described are certain diallylic ethers defined according to the generic structure: ##STR6##

This is a divisional of application Ser. No. 602,646, filed 4/20/84 nowU.S. Letters Pat. No. 4,548,743 issued on Oct. 22, 1985.

BACKGROUND OF THE INVENTION

U.S. Pat. Nos. 4,064,281 issued Dec. 20, 1977 and 4,102,928 issued July25, 1978 describe processes for preparing compounds defined according tothe structure: ##STR7## in low yields by reaction of an allylic halidewith acetyl-3,3-dimethylcyclohexane in the presence of a phase transfercatalyst. Primarily U.S. Pat. No. 4,064,281 teaches the reaction:##STR8## (wherein X is chloro or bromo and M is alkali metal). Thecompound having the structure: ##STR9## is prepared incidentally to thatreaction. Dutch Published application No. 7500838 discloses thepreparation of the compound having the structure: ##STR10## in a mannerdifferent in kind from the instant process giving rise to yields farbelow the yields produced according to the instant process and disclosesits use in perfumery and in augmenting foodstuff flavors. The perfumeryuse of this compound and other members of its class is described as"floral, green, herbaceous and chypre". The use as a galbanum componentis also disclosed therein.

Furthermore, allyl alpha and beta ionones are known for their uses inaugmenting or enhancing the organoleptic properties of consumablematerials such as foodstuffs, chewing gums, medicinal products,perfumes, perfume compositions, colognes and perfumed articles. Thus,Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", Volume I,1969, at Monograph 86 indicates that allyl ionone ("alpha allyl ionone")having the structure: ##STR11## has an oily-sweet, slightly flowery butalso fruity, woody and bark-like, green odor of considerable tenacity.Arctander further states that this compound is "useful in perfumecompositions as a modifier for ionones and methyl ionones, inmodern-aldehydic creations, in perfumes with fruity-alkehydic topnotes,in combination with vetiver or woody-floral perfume materials, etc.".Arctander further states that the compound is "used in flavors--intraces--for imitation raspberry and pineapple". Arctander further statesthat is compound is produced from citral by condensation with allylacetone, followed by cyclization.

There is a need to produce such allyl alpha and beta ionones in aninexpensive manner and in high purity whereby they can be more readilyused in augmenting or enhancing the organoleptic properties ofconsumable materials.

The Claisen rearrangement of allylic ethers is well documented in theliterature. Thus, Denmark et al, J. Am. Chem. Soc. 1982, 104, 4972entitled "Carbanion-accelerated Claisen Rearrangements" discloses thereaction: ##STR12## wherein X could represent alkyl and R¹ and R² can bethe same or different methyl or hydrogen.

Daub, et al, "Tetrahedron Letters", 1983, 24(41), at pages 4397-4400,entitled "Ketal Claisen Rearrangements of Functionalized Ketals"(abstracted at Chem. Abstracts, Volume 100, 1984, No. 67808W) disclosesthe reaction: ##STR13## taking place in the presence of propionic acidas a catalyst wherein R₁ represents phenyl or n-propyl and R₂ representsmethoxycarbonyl, methoxyacetyl or ethenyl. Daub, et al, discloses thatin all cases the product having the structure: ##STR14## is in themajority as opposed to the compound having the structure: ##STR15## Hurdand Pollack, J. Am. Chem. Soc. 60, 1938, page 1905 discloses thereactions: ##STR16## and the Merck Index, 10th edition, 1983, disclosesthe "Claisen" Rearrangement", to wit:

The above-mentioned "Claisen" rearrangement was originally disclosed inBer. 45, 3157 (1912), to wit: ##STR17##

Nothing in the prior art, however, indicates the selectivity of therearrangement of a member of the genus of compounds defined according tothe structure: ##STR18## to a corresponding member of the genus ofcompounds having the structure: ##STR19## over a corresponding member ofthe genus of compounds having the structure: ##STR20## in the presenceof a basic catalyst at a pH in the range of from about 7 up to about 11in all cases except those involving the Claisen rearrangement ofcompounds belonging to the genus defined according to the structure:##STR21## or in the presence of an acidic catalyst at a pH in the rangeof from about 2 up to about 6.5 in the case of the rearrangement of amember of the genus defined according to the structure: ##STR22## to amember of the genus defined according to the structure: ##STR23## over amember of the genus defined according to the structure: ##STR24##wherein R₆, R₇ and R₈ are defined, supra.

Chemical compounds which can provide galbanum-like, woody, piney,floral, green, herbaceous, chypre-like, sweet, fruity, raspberry-like,jasmin, rosey, pear-like, licorice-like, aniseed-like and bark-likearoma profiles with jasmin, green, cedarwood, minty, citrusy, lemony andcamphoraceous topnotes are highly desirable in the art of perfumery.Many of the natural materials which provide such fragrances andcontribute such desired nuances to perfumery compositions and perfumedarticles are high in cost, unobtainable at times, vary in quality fromone batch to another and/or are generally subject to the usualvariations in natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the fragrance notes provided bynatural essential oils or compositions thereof. Unfortunately, many ofthe synthetic materials either have the desired nuances only to arelatively small degree or they contribute undesirable or unwanted odorto the compositions.

Our invention fulfills the need for production of allyl alpha and betaionones as well as 1-pentenoyl cyclohexane derivatives and other suchasymmetrical ketones by the creation of syntheses of such asymmetricketones inexpensively and directed towards the creation of specificderivatives.

Our invention also fulfills the need for production of materials havingthe above-identified aroma nuances including perfume compositions,colognes and perfumed articles which include but are not limited tosolid or liquid anionic, cationic, nonionic and zwitterionic detergents,fabric softener compositions, fabric softener articles and perfumedpolymers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the NMR spectrum for fraction 9 of the distillation of thereaction product of Example I containing the compound having thestructure: ##STR25## (Conditions: Field strength: 100 MHz; solvent:CFCl₃)

FIG. 2 is the NMR spectrum for the compound having the structure:##STR26## produced according to Example II (Conditions: Field strength:100 MHz; solvent: CFCl₃).

FIG. 3 is the GLC profile for the crude reaction product of Example IVcontaining the compounds having the structures: ##STR27##

FIG. 4 is the GLC profile for the bulked fractions 9-20 of thedistillation of the reaction product of Example V containing thecompounds having the structures: ##STR28##

FIG. 5 is the GLC profile for the crude reaction product of ExampleVI(c) containing the compound having the structure: ##STR29##

FIG. 6 is the GLC profile for the crude reaction product of Example VIIcontaining the compounds having the structures: ##STR30##

FIG. 7 is the GLC profile for fraction 6 of the distillation of thereaction product of Example VII containing the compounds having thestructures: ##STR31##

FIG. 8 is the NMR spectrum for fraction 5 of the distillation of thereaction product of Example VII containing the compounds having thestructures: ##STR32## (Solvent: CFCl₃ ; field strength: 100 MHz).

FIG. 9 is the GLC profile for the crude reaction product of Example VIIIcontaining the compounds having the structures: ##STR33##

FIG. 10 is the infra-red spectrum for the compounds having thestructures: ##STR34## produced according to Example VIII.

FIG. 11 is the NMR spectrum for fraction 19 of the distillation of thereaction product of Example VIII containing the compound having thestructure: ##STR35## (Conditions: Field strength: 100 MHz; solvent:CFCl₃).

FIG. 12 is the NMR spectrum for fraction 8 of the distillation of thereaction product of Example VIII containing the compound having thestructure: ##STR36## (Conditions: Field Strength: 100 MHz; solvent:CFCl₃).

FIG. 13 is the GLC profile for the crude reaction product of Example IXcontaining the compounds having the structures: ##STR37##

FIG. 14 is the NMR spectrum for fraction 10 of the distillation of thereaction product of Example IX containing the compound having thestructure: ##STR38## (Conditions: Field strength: 100 MHz; solvent:CFCl₃).

FIG. 15 is the GLC profile for the crude reaction product of ExampleX(A) containing the compounds having the structures: ##STR39##

FIG. 16 is the GLC profile for bulked fractions 7-15 inclusive, for thesecond distillation of the reaction product of Example X(A) containingthe compounds having the structures: ##STR40##

FIG. 17 is the GLC profile for the crude reaction product of ExampleX(B) containing the compounds having the structures: ##STR41## with avery minor proportion of compound having the structure: ##STR42##

FIG. 18 is the GLC profile for fraction 14 of the second distillation ofthe reaction product of Example X(B) containing the compounds having thestructures: ##STR43##

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 3 is the GLC profile for the crude reaction product of Example IVcontaining the compounds having the structures: ##STR44## (Conditions:SE-30 column programmed at 180° C. isothermal). The peak indicated byReference Numeral 30 is the peak for the compound having the structure:##STR45## The peak indicated by Reference Numeral 31 is the peak for thecompound having the structure: ##STR46##

FIG. 4 is the GLC profile for bulked fractions 9-20 of the distillationof the reaction product of Example V containing the compounds having thestructures: ##STR47## The peaks indicated by Reference Numerals 40 and41 are the peaks for the compounds having the structures: ##STR48##individually.

FIG. 5 is the GLC profile for the crude reaction product of ExampleVI(c). The peak indicated by Reference Numeral 50 is the peak for thecompound having the structure: ##STR49##

FIG. 13 is the GLC profile for the crude reaction product of Example IXcontaining the compounds having the structures: ##STR50## (Conditions:SE-30 column programmed at 160° C. isothermal). The peak indicated byReference Numeral 130 is the peak for the compounds having thestructures: ##STR51##

THE INVENTION

The invention broadly relates to compounds defined according to thegeneric structure: ##STR52## wherein one of Z₁ or Z₂ is the moiety:##STR53## and the other of Z₁ or Z₂ represents hydrogen; wherein R₁₁ andR₂₁ represents hydrogen or the same or different alkyl or alkenyl

with the proviso that R₁₁ and R₂₁ are not both hydrogen or R₁₁ and R₂₁taken together:

(i) complete a cycloalkyl, cycloalkenyl, bicycloalkyl, mono or polyalkylcycloalkyl, mono or polyalkyl cycloalkenyl ring, or

(ii) represent alkylidene, cycloalkenyl alkylidene, aralkylidene, monoor polyalkyl cycloalkenyl alkylidene or mono or polyalkyl aralkylidene;

and wherein R₆, R₇ and R₈ are the same or different and each representshydrogen or methyl.

Broadly, our invention relates to a process for producing the compoundsdefined according to the genus: ##STR54## which are hereinafter referredto as "asymmetric ketones". Such a process is an "isomer-directedprocess" which involves a Claisen rearrangement of diallylic etherswhich in turn are produced by means of reacting an allylic alcohol witha dialkyl ketal of a ketone.

More specifically, the asymmetric ketones of our invention genericallydefined according to the structure: ##STR55## are prepared by firstreacting a ketone defined according to the structure: ##STR56## whereinR₁₁ and R₂₁ are defined, supra, with a trialkylorthoformate definedaccording to the structure: ##STR57## wherein R₁, R₂ and R₃ are the sameor different and each represents C₁ -C₃ lower alkyl according to thereaction: ##STR58## whereby the compound having the structure: ##STR59##is formed wherein R₄ and R₅ are each one of R₁, R₂ and R₃. The resultingdialkyl ketal defined according to the structure: ##STR60## may then beused "as is" for its perfumery properties or for augmenting or enhancingthe aroma of the perfume composition, cologne or perfumed article, e.g.,solid or liquid anionic, cationic, nonionic or zwitterionic detergent,perfumed polymer, fabric softener composition or fabric softener articleor it may be further reacted with an allyl alcohol defined according tothe structure: ##STR61## wherein R₆, R₇ and R₈ are as defined, supra.

This reaction takes place in the presence of an acid or base dependingupon the desired ratio of ultimate asymmetric ketone desired. Forproducing a number of isomers specified herein, the reaction takes placeusing an acidic catalyst as disclosed in the prior art. See Daub, et al,cited, supra. For producing isomers covered by the generic structures:##STR62## the reaction is not so disclosed.

In any event, the reaction involving the Claisen rearrangement takingplace at a pH of between 7 and 11 is a novel reaction giving rise tounexpected, unobvious and advantageous results.

In the first part of the reaction of the allylic alcohol with a dialkylketal, the diallyl ketal defined according to the structure: ##STR63##is formed.

A number of the diallyl ketals created using the foregoing process arenovel.

The resulting diallyl ketal then rearranges to form two compounds whichare members of the following two genera:

(i) the genus defined according to the structure: ##STR64##

(ii) the genus defined according to the structure: ##STR65##

Depending upon the pH of the reaction mass during the rearrangement andthe nature of R₁₁ and R₂₁ as hereinafter specified, the rearrangementforms a preponderant amount of a compound which is a member of thegenus: ##STR66## or a preponderant amount of a member of the genushaving the structure: ##STR67##

Specifically, when the reaction is carried out at a pH in the range offrom about 7 up to about 11 (using, for example, sodium acetate) withthe exception of that situation where the precursor ketone has thestructure: ##STR68## and the corresponding diallyl ketal precursor genushas the structure: ##STR69## a preponderant amount of compound withinthe genus having the structure: ##STR70## is formed.

When the reaction is carried out at a pH in the range of from about 2 upto about 6.5 (for example, using an acidic catalyst such as citric acid)with the exception of that situation where the precursor ketone has thestructure: ##STR71## and the corresponding diallyl ketal genus has thestructure: ##STR72## a preponderant amount of genus defined according tothe structure: ##STR73## is formed.

On the contrary, when using an acidic catalyst with the precursor ketonehaving the structure: ##STR74## which gives rise to the diallyl ketalgenus having the structure: ##STR75## a preponderant amount of genusdefined according to the structure: ##STR76## is formed.

The mechanism of the rearrangement of the compound having the structure:##STR77## is as follows: ##STR78## whereby the compound having thestructure: ##STR79## is formed.

The mechanism of the rearrangement of the compound having the structure:##STR80## is thusly: ##STR81## whereby the compound having thestructure: ##STR82## is formed.

In summary, the reaction of the allylic alcohol with a dialkyl ketal toform the diallyl ketal is thusly: ##STR83##

With the exception stated, supra, concerning the diallyl ketal genusdefined according to the structure: ##STR84## the rearrangement of thediallyl ketal follows the following reaction course (preponderantly) ina reaction mass at a pH of from 7 up to about 11 (basic) thusly:##STR85##

With the exceptions stated, supra (and exemplified in Example X(A),infra), the reaction sequence is preponderantly as follows in an acidicreaction medium, e.g., using a propionic or citric acid catalyst:##STR86##

In the reaction to form the dialkyl ketal, to wit: ##STR87## thereaction temperature is in the range of from about -10° C. up to about50° C.

The mole ratio of ketone having the structure: ##STR88## totrialkylorthoformate having the structure: ##STR89## is from about 1:1up to about 1:2.

When using an acid catalyst, various acids can be used, e.g., propionicacid, citric acid, hydrochloric acid, or any other Lewis or protonicacid. The preferred mole percent of acid catalyst is from about 0.01mole percent up to about 0.10 mole percent but when using an acidiccatalyst the pH of the reaction mass including that existing during theClaisen rearrangement must be between about 2 and about 6.5.

When using a basic medium, the preferred basic catalyst is an alkalimetal alkanoate, for example, sodium acetate, potassium acetate,potassium formate, sodium formate, sodium propionate, potassiumpropionate, sodium butyrate or potassium butyrate. The mole percent ofbase in the reaction mass may vary from about 0.01 percent up to about0.40 mole percent, but when using a basic catalyst, the reaction massmust be maintained at a pH of between 7 and 11.

In carrying out the reaction to form the dialkyl ketal, all the reagentsare charged to the reaction mass and the alkyl formate, formed byreaction, is removed by means of distillation. The organic phase iswashed and dried over a molecular sieve or anhydrous magnesium sulfate.The crude ketal may be used "as is" for its perfumery properties or itmay be further reacted with the allylic alcohol defined according to thestructure: ##STR90## according to the reaction: ##STR91##

The thus-formed diallyl ether is preferably not isolated but remains inthe reaction mass and is rearranged via the Claisen rearrangement (inacidic or basic media, as desired) according to the reactions: ##STR92##

The mole ratio of dialkyl ketal defined according to the structure:##STR93## to allylic alcohol defined according to the structure:##STR94## may vary from about 1:1 up to about 1:3 with a mole ratio ofdialkyl ketal:allylic alcohol of about 1:2 being preferred.

The reaction temperature may vary from about 120° C. up to 220° C. witha reaction temperature of about 150° C. being preferred.

Following the rearrangement reaction, the reaction mass is preferablynot washed but distilled directly with the allylic alcohol definedaccording to the structure: ##STR95## being recycled.

As an example of the application of the foregoing reaction conditions,when the reaction of our invention takes place with a rearrangement ofthe diallylic ether defined according to the structure: ##STR96## at150° C., two compounds are formed, the first having the structure##STR97## and the second having the structure: ##STR98##

When using the citric acid catalyst, the mole ratio of the compoundhaving the structure: ##STR99## to the compound having the structure:##STR100## is 1:4. When using no catalyst, the mole ratio of compoundhaving the structure: ##STR101## to the compound having the structure:##STR102## is 4:6. When using the sodium acetate catalyst the mole ratioof the compound having the structure: ##STR103## to the compound havingthe structure: ##STR104## is 20:1.

Another example of the application of the foregoing reaction conditionswhen the reaction of our invention takes place with a rearrangement ofthe dialyllic ether defined according to the structure: ##STR105## at150° C., three compounds are formed, now the first having the structure:##STR106## the second having the structure: ##STR107## and the thirdhaving the structure: ##STR108##

When using the citric acid catalyst, the mole ratio of the compoundhaving the structure: ##STR109## to the sum total of compounds havingthe structures: ##STR110## is about 48:1.

On the contrary, an additional example of the application of theforegoing reaction conditions exists when the reaction of our inventiontakes place with a rearrangement of the diallylic ether definedaccording to the structure: ##STR111## at 150° C. where four compoundsare formed, the first having the structure: ##STR112## the second havingthe structure: ##STR113## the third having the structure: ##STR114## andthe fourth having the structure: ##STR115##

When using the citric acid catalyst, compounds having the structures:##STR116## are predominant in the reaction mass and compounds having thestructures: ##STR117## are present in the reaction mass in very smallquantities.

Examples of compounds produced according to our process and theirorganoleptic properties are as follows:

                  TABLE I                                                         ______________________________________                                        COMPOUND STRUCTURE                                                                              PERFUMERY PROPERTIES                                        ______________________________________                                         ##STR118##       A galbanum-like, floral, green, herbaceous and chypre                         aroma profile.                                              Mixture of compounds having                                                                     A woody, piney, floral aroma                                the structures:   with citrusy, lemony topnotes.                               ##STR119##                                                                   and                                                                            ##STR120##                                                                   the mole ratio of (i) to (ii) being                                           1:4.                                                                           ##STR121##       A sweet, fruity, raspberry- like, jasmin, floral and                          rosey aroma with jasmin top- notes.                         and                                                                            ##STR122##                                                                   the mole ratio of (i) to (ii) being                                           being 1:4.                                                                     ##STR123##       A sweet, pear and fruity aroma with green, cedarleaf                          and minty topnotes.                                          ##STR124##       A licorice and aniseed aroma with fruity, pineapple,                          green, woody, herbaceous, minty and camphoraceous top-                        notes.                                                      and                                                                            ##STR125##                                                                   the mole ratio of (i) to (ii)                                                 being 1:4.                                                                     ##STR126##       A sweet, floral, fruity, bark-like and green aroma                            profile.                                                     ##STR127##                                                                    ##STR128##                                                                   with the mole ratio of (i) to the                                             sum total of (ii) and (iii) being                                             48:1                                                                          ______________________________________                                    

The asymmetric ketones and ketals of our invention and one or moreauxiliary perfume ingredients including, for example, alcohols,aldehydes, ketones other than the asymmetric ketones of our invention,ketals other than the asymmetric ketals of our invention, terpinichydrocarbons, nitriles, esters, lactones, natural essential oils andsynthetic essential oils, may be admixed so that the combined odors ofthe individual components produce a pleasant and desired fragrance,particularly and preferably in galbanum, jasmin and floral fragrances.

Such perfume compositions usually contain:

(a) the main note or the "bouquet" or foundation stone of thecomposition;

(b) modifiers which round off and accompany the main notes;

(c) fixatives which include odorous substances which lend a particularnote to the perfume throughout all stages of evaporation and substanceswhich retard evaporation; and

(d) topnotes which are usually low boiling fresh smelling materials.

In perfume compositions, it is the individual olfactory components whichcontribute to their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, theasymmetric ketones and ketals of our invention can be used to alter,modify or enhance the aroma characteristics of a perfume composition,for example, by utilizing or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of asymmetric ketones and ketals of our invention which willbe effective in perfume compositions as well as in perfumed articles andcolognes, depends upon many factors, including the other ingredients,their amounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of the asymmetricketones and/or ketals or even less (e.g., 0.005%) can be used to impartgalbanum-like, woody, piney, floral, green, herbaceous, chypre, sweet,fruity, raspberry-like, jasmin, rosey, licorice, aniseed and bark-likearomas with jasmin, green, cedarleaf, minty, citrusy, lemony, fruity,pineapple, woody, herbaceous and camphoraceous topnotes to soaps,cosmetics, solid or liquid anionic, cationic, nonionic or zwitterionicdetergents, perfumed polymers or other products. The amount employed canrange up to 70% of the fragance components and will depend upon theconsiderations of cost, nature of the end product, the effect desired onthe finished product and the particular fragrance sought.

The asymmetric ketones and/or ketals of our invention are useful asolfactory components in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, bath preparations, such aslacquers, brilliantines, pomades and shampoos; cosmetic preparations,such as creams, deodorants, hand lotions and sun screens; powders, suchas talcs, dusting powders, face powders and the like. When used as anolfactory component in a perfumed article as little as 0.1% of theasymmetric ketone or ketal will suffice to impart intense galbanum-like,woody, piney, floral, green, herbaceous, chypre, sweet, fruity,raspberry-like, jasmin, rosey, pear-like, licorice, aniseed-like andbark-like aroma profiles with jasmin, green, cedarleaf, minty, citrusy,lemony, fruity, pineapple, woody, herbaceous and camphoraceous topnotesto various galbanum, rose, floral and jasmin formulations. Generally, nomore than 3% of the asymmetric ketone or ketal based on the ultimate endproduct is required in the perfumed article. Thus, the range of use ofthe asymmetric ketones and/or ketals of our invention in perfumedarticles may vary from 0.1% up to about 3%.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for the asymmetric ketones orketals of our invention. The vehicle can be a liquid, such as analcohol, such as ethy alcohol, a glycol, such as propylene glycol or thelike. The carrier can also be an absorbant solid, such as a gum (e.g.,gum arabic, guar gum and xanthan gum) or components for encapsulatingthe composition (such as gelatin when encapsulation is carried on bymeans of coacervation, or such as a urea formaldehyde prepolymer when aurea formaldehyde polymer wall is formed around a perfumed scenter).

The following examples serve to illustrate our invention and theinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given are by weight unless otherwisespecified.

EXAMPLE I FORMATION OF DIMETHYL KETAL OF 1-ACETYL-3,3-DIMETHYLCYCLOHEXANE Reaction ##STR129##

Into a 12 liter reaction flask equipped with stirrer, thermometer,reflux condenser, bidwell collection trap and heating mantle are place1848 grams of 1-acetyl-3,3-dimethyl cyclohexane and 24 ml. concentratedhydrochloric acid.

Over a period of 10 minutes, 1908 grams of trimethylorthoformate isadded to the reaction mass while maintaining the temperature at 23°-37°C. The reaction mass is then heated after the addition to a temperaturein the range of 80°-90° C. and maintained at that temperature for aperiod of three hours. At the end of the three hour period 50 grams ofsodium acetate is added to the reaction mass. The reaction mass isstirred and 1 liter of water is added. The organic layer is separatedfrom the aqueous layer and the organic layer is distilled on a 12"×1"Goodloe column yielding the following fractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         35/55       70/82    4.0/4.0                                        2         55          87       4.0                                            3         60          87       4.0                                            4         65          88       4.0                                            5         73          90       4.0                                            6         73          90       4.0                                            7         73          90       4.0                                            8         73          90       4.0                                            9         73          90       4.0                                            10        73          90       4.0                                            11        73          110      4.0                                            12        50          225      1.0                                            ______________________________________                                    

FIG. 1 is the NMR spectrum for fraction 9 of the foregoing distillationcontaining the compound having the structure: ##STR130## (Conditions:CFCl₃ solvent; 100 MHz field strength).

The resulting product has an excellent sweet, pear, fruity aroma profilewith green, cedarleaf and minty topnotes.

EXAMPLE II PREPARATION OF DIETHYL KETAL OF 1-ACETYL-3,3-DIMETHYLCYCLOHEXANE Reaction ##STR131##

Into a 5 liter reaction flask equipped with stirrer, thermometer, refluxcondenser, bidwell trap apparatus, addition funnel and heating mantleare placed 1232 grams of 1-acetyl-3,3-dimethyl cyclohexane and 18 ml.concentrated hydrochloric acid. Over a period of one hour whilemaintaining the reaction temperature at 20°-35° C., 1480 grams oftriethylorthoformate is added to the reaction mass. The reaction mass isthen stirred for a period of three hours while maintaining thetemperature at 90°-110° C. At the end of the three hour period thereaction mass is cooled to 20° C. and 50 grams of sodium carbonate isadded. 1 Liter of water is then added and the organic phase is separatedfrom the aqueous phase.

FIG. 2 is the NMR spectrum for the resulting product (conditions: Fieldstrength: 100 MHz; solvent: CFCl₃).

EXAMPLE III PREPARATION OF 1-(4-PENTENOYL)-3,3-DIMETHYL CYCLOHEXANEReaction ##STR132##

Into a 2 liter autoclave is placed 672 grams of the dimethyl ketal of1-acetyl-3,3-dimethyl cyclohexane prepared according to Example I; 348grams of allyl alcohol; and 15 grams of sodium acetate. The autoclave issealed and the contents are heated to 150° C. and maintained at 150° C.for a period of five hours. At the end of the five hour period theautoclave contents are cooled and the autoclave is opened. The resultingproduct is distilled on a 12" Goodloe column yielding the followingfractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         50/50       80/80    3.0                                            2         50           82      3.0                                            3         50           82      3.0                                            4         56           87      3.0                                            5         53           88      3.0                                            6         55           95      3.0                                            7         55           98      3.0                                            8         64          100      3.0                                            9         64          100      3.0                                            10        64          100      3.0                                            11        80          109      3.0                                            12        80          109      3.0                                            13        90          109      3.0                                            14        90          109      3.0                                            15        80          109      1.6                                            16        80          109      1.6                                            17        71          112      0.8                                            18        71          116      0.8                                            19        72          128      0.8                                            20        74          168      0.8                                            21        76          235      0.8                                            22        50          240      0.8                                            ______________________________________                                    

The mole ratio of isomers in the reaction mass is 20:1 of the compoundhaving the structure: ##STR133## to the compound having the structure:##STR134##

The peak indicated by Reference Numeral 30 is the peak for the compoundhaving the structure: ##STR135## The peak indicated by Reference Numeral31 is the peak for the compound having the structure: ##STR136##

The resulting reaction mixture has an intense galbanum aroma withfloral, green, herbaceous and chypre undertones.

EXAMPLE IV PREPARATION OF 1-(4-PENTENOYL)-3,3-DIMETHYL CYCLOHEXANEReaction R1 ? ##STR137##

Into a 2 liter autoclave is placed 700 grams of the diethyl ketal of1-acetyl-3,3-dimethyl cyclohexane prepared according to Example II; 360grams of allyl alcohol; and 10 grams of sodium acetate. The autoclave issealed and heated to 150° C. and maintained at that temperature for aperiod of five hours. At the end of the five hour period, the autoclaveis opened and the contents are filtered, washed with water and distilledon a 12" Goodloe column yielding the following fractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         47/42       100/91   1.2/9                                          2         56           94      0.9                                            3         68          105      0.9                                            4         70          106      0.9                                            5         71          105      0.9                                            6         70          101       0.85                                          7         70          102       0.85                                          8         70          102       0.85                                          9         70          102       0.85                                          10        79          105      0.9                                            11        79          110      0.9                                            12        79          108      0.8                                            13        79          108      0.8                                            14        79          110      0.8                                            15        79          130      0.8                                            16        65          170      0.8                                            ______________________________________                                    

FIG. 3 is the GLC profile for the crude reaction product. The peakindicated by Reference Numeral 30 is the peak for the compound havingthe structure: ##STR138## The peak indicated by Reference Numeral 31 isthe peak for the compound having the structure: ##STR139##

The resulting product has an intense galbanum-like, floral, green,herbaceous and chypre aroma.

The ratio of isomer having the structure: ##STR140## to the isomerhaving the structure: ##STR141## is 20:1.

EXAMPLE V PREPARATION OF MIXTURE OF ISOMERS:1-(4-PENTENOYL)-3,3-DIMETHYL CYCLOHEXANE AND1-ACETYL-1-(2-PROPENYL)-3,3-DIMETHYL CYCLOHEXANE Reaction ##STR142##

Into a 2 liter autoclave is placed 672 grams (3 moles) of the dimethylketal of 1-acetyl-3,3-dimethyl cyclohexane prepared according to ExampleI; 348 grams (6 moles) allyl alcohol; and 0.5 grams of citric acid. Theautoclave is heated to 150° C. and maintained at that temperature underpressure for a period of two hours. At the end of the two hour period,the contents of the autoclave is cooled, the autoclave is opened and thecontents are filtered and distilled yielding the following fractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         23/58       23/85    300/200                                        2         80          105      6.0                                            3         60           90      4.0                                            4         60          100      4.0                                            5         82          105      4.0                                            6         83          106      4.0                                            7         83          108      4.0                                            8         84          109      4.0                                            9         85          110      4.0                                            10        90          110      4.0                                            11        90          112      4.0                                            12        90          112      4.0                                            13        90          114      4.0                                            14        90          114      4.0                                            15        90          114      4.0                                            16        90          114      4.0                                            17        90          115      4.0                                            18        90          115      4.0                                            19        90          116      4.0                                            20        89          178      3.0                                            21                                                                            ______________________________________                                    

FIG. 4 is the GLC profile for the bulked fractions 9-20 of the foregoingdistillation containing the compounds having the structures: ##STR143##The isomer ratio of the compound having the structure: ##STR144## to thecompound having the structure: ##STR145## is 1:4. The resulting producthas a galbanum-like, amber aroma with floral and jasmin topnotes.

EXAMPLE VI PREPARATION OF MIXTURES OF ISOMERS OR1-(4-PENTENOYL)-3,3-DIMETHYL CYCLOHEXANE AND1-ACETYL-1-(2-PROPENYL)-3,3-DIMETHYL CYCLOHEXANE Reaction ##STR146##

The following Table II sets forth reactants including catalyst, reactionconditions and ratio of isomer having the structure: ##STR147## toisomer having the structure: ##STR148## using the procedure of ExampleIII.

                                      TABLE II                                    __________________________________________________________________________                                        RATIO OF ISOMER HAVING THE                                                    STRUCTURE:                                                                     ##STR149##                                                                   TO ISOMER HAVING THE STRUCTURE:            NO.EXAMPLE                                                                            AMOUNTSCATALYST ANDREACTANTS AND                                                              CONDITIONSREACTION                                                                        ##STR150##                               __________________________________________________________________________    EXAMPLE Dimethyl ketal of 1-acetyl-3,3-                                                               150° C. and three hours                                                            11:6                                      VI(a)   dimethyl cyclohexane-672 grams                                                Citric acid-0.5 grams                                                         Allyl alcohol-350 grams                                               EXAMPLE Dimethyl ketal of 1-acetyl-3,3-                                                               150° C. and six hours                                                              3:2                                       VI(b)   dimethyl cyclohexane-672 grams                                                Triethanolamine-10 grams                                                      Diallyl alcohol-350 grams                                             EXAMPLE Dimethyl ketal of 1-acetyl-3,3-                                                               150° C. and six hours                                                              12:17                                     VI(c)   dimethyl cyclohexane-672 grams                                                Catalyst: NONE                                                                Allyl alcohol-350 grams                                               EXAMPLE Dimethyl ketal of 1-acetyl-3,3-                                                               150° C. and six hours                                                              12:17                                     VI(d)   dimethyl cyclohexane-672 grams                                                Sodium carbonate-10 grams                                                     Allyl alcohol-350 grams                                               EXAMPLE Dimethyl ketal of 1-acetyl-3,3-                                                               150° C. and six hours                                                               1:20                                     VI(e)   dimethyl cyclohexane-672 grams                                                Sodium acetate-10 grams                                                       Allyl alcohol-350 grams                                               __________________________________________________________________________

FIG. 5 is the GLC profile for the crude reaction product of ExampleVI(c). The peak indicated by Reference Numeral 50 is the peak for thecompound having the structure: ##STR151##

EXAMPLE VII Preparation of mixture of1-(3,3-DIMETHYL-4-PENTENOYL)-3,3-DIMETHYL CYCLOHEXANE and1-ACETYL-1-(1,1-DIMETHYL-2-PROPENYL)-3,3-DIMETHYL CYCLOHEXANE Reaction##STR152##

Into a 2 liter autoclave is placed 400 grams of the diethyl ketal of1-acetyl-3,3-dimethyl cyclohexane prepared according to Example II; 516grams of prenol; and 0.5 grams of citric acid. The autoclave is sealedand heated to 150° C. under pressure and maintained at 150° C. for aperiod of two hours. At the end of the two hour period the autoclave iscooled, opened and the contents are filtered and distilled on a 12"Goodloe column yielding the following fractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         70/80       116/110  5.0/1.0                                        2         85          115      1.0                                            3         85          125      1.0                                            4         85          145      1.0                                            5         80          190      1.0                                            6         87          230      1.0                                            ______________________________________                                    

FIG. 6 is the GLC profile of the crude reaction product containing thecompounds having the structures: ##STR153##

FIG. 7 is the GLC profile for fraction 6 of the foregoing distillationcontaining the compounds having the structures: ##STR154##

The resulting product has a woody, piney, floral aroma with citrusy andlemony topnotes.

EXAMPLE VIII PREPARATION OF MIXTURE OF 7-PHENYL-1-HEPTEN-5-ONE AND4(PHENYL METHYL)1-PENTEN-5-ONE Reactions ##STR155##

Into a 2 liter reaction flask equipped with stirrer, thermometer, refluxcondenser, addition funnel, bidwell trap and heating mantel is placed400 grams of benzyl acetone and 5 ml. concentrated hydrochloric acid.Over a period of 30 minutes, 339 grams of trimethylorthoformate isadded. The reaction mass is then heated to 60° C. and maintained at 60°C. for a period of two hours with stirring.

The reaction mass is then cooled to room temperature and 10 grams ofsodium carbonate is added followed by 300 ml. of water. The organicphase is separated from the aqueous phase.

The organic phase is then placed in an autoclave and 350 ml. allylalcohol and 1 gram citric acid is added. The autoclave is sealed andheated under pressure to 150° C. The reaction mass is maintained at 150°C. under pressure in the autoclave for a period of two hours. Theautoclave is then cooled, opened and the contents filtered.

The reaction mass is distilled on a 12" Goodloe column yielding thefollowing fractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         26/26       50/68    1.5                                            2         70          114      1.4                                            3         72          119      0.9                                            4         87          120      0.9                                            5         89          122      0.8                                            6         90          122      0.8                                            7         88          122      0.8                                            8         89          122      0.8                                            9         89          122      0.8                                            10        89          122      0.8                                            11        89          122      0.8                                            12        86          116      0.8                                            13        86          118      0.8                                            14        86          118      0.8                                            15        88          118       0.85                                          16        95          120       0.95                                          17        95          122       0.90                                          18        100         130      1.0                                            19        110         187      1.6                                            20        110         200      1.0                                            ______________________________________                                    

FIG. 9 is the GLC profile for the crude reaction product.

FIG. 10 is the infra-red spectrum for the compound having the structure:##STR156##

FIG. 11 is the NMR spectrum for fraction 19 of the foregoingdistillation for the compound having the structure: ##STR157##(Conditions: Field strength: 100 MHz; solvent: CFCl₃).

FIG. 12 is the NMR spectrum for fraction 8 of the foregoing distillationfor the compound having the structure: ##STR158## (Conditions: Fieldstrength: 100 MHz; solvent: CFCl₃).

Bulked fractions 8-20 containing the compounds having the structures:##STR159## has a sweet, fruity, raspberry-like, jasmin, floral and roseyaroma with jasmin topnotes. The ratio of compounds having the structure:##STR160## to the compound having the structure: ##STR161## is 1:4.

EXAMPLE IX PREPARATION OF MIXTURE OF 1-UNDECEN-5-ONE AND4-(1-PENTYL)-1-HEXEN-5-ONE Reactions ##STR162##

Into a 2 liter reaction flask equipped with stirrer, thermometer, refluxcondenser, bidwell trap, and heating mantle is placed 624 grams ofmethyl hexyl ketone and 8 ml. concentrated hydrochloric acid. Over aperiod of 30 minutes 530 grams of trimethylorthoformate is added to thereaction mass. The reaction mass is then maintained with stirring at atemperature of 60° C. for a period of three hours. At the end of thethree hour period, 10 grams of sodium carbonate is added to the reactionmass and, with stirring, 300 ml. water is added to the reaction mass.The organic phase is separated from the aqueous phase and the organicphase is placed in a 2 liter autoclave.

Also, 406 grams of allyl alcohol and 1 gram of citric acid is added tothe autoclave. The autoclave is then sealed and heated to 150° C. underpressure and maintained at 150° C. under pressure for a period of twohours. At the end of the two hour period the autoclave is cooled, openedand the contents filtered. The contents are then distilled on a 12"Goodloe column yielding the following fractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         28/45       50/68    8.0                                            2         55          70       8.0                                            3         30          52       1.6                                            4         30          55       1.6                                            5         30          55       3.0                                            6         35          52       1.8                                            7         30          52       1.6                                            8         30          52       1.6                                            9         38          63       4.0                                            10        45          70       6.0                                            11        45          73       6.0                                            12        45          78       6.0                                            13        48          80       6.0                                            14        62          80       6.0                                            15        76          86       6.0                                            16        75          85       6.0                                            17        75          85       6.0                                            18        75          85       6.0                                            19        75          85       6.0                                            20        75          85       6.0                                            21        75          87       6.0                                            22        75          112      6.0                                            23        60          230      6.0                                            ______________________________________                                    

FIG. 13 is the GLC profile for the crude reaction product (conditions:SE-30 column programmed at 160° C. isothermal). The peak indicated byReference Numeral 130 is the peak for the compounds having thestructures: ##STR163##

FIG. 14 is the NMR spectrum for fraction 10 of the foregoingdistillation containing the compound having the structure: ##STR164##(Conditions: Solvent: CFCl₃ ; field strength: 100 MHz).

Bulked fractions 17-22 of the foregoing distillation has a licorice,aniseed aroma with fruity, pineapple, green, woody, herbaceous, mintyand camphoraceous topnotes. The isomer ratio of bulked fractions 17-22of the compound having the structure: ##STR165## the compound having thestructure: ##STR166## is 1:4.

EXAMPLE X(A) PREPARATION OF ALLYL ALPHA IONONE ISOMER MIXTURE Reactions##STR167##

Into a 5 liter reaction flask equipped with stirrer, thermometer,addition funnel, bidwell trap, heating mantle, cooling bath and refluxcondenser is placed 640 grams (20 moles) of methanol, 1520 grams (8.0moles) of alpha ionone and 934 grams (8.8 moles) oftrimethylorthoformate. The reaction flask is cooled to -10° C. andmaintained at -10° C. to -20° C. Over a period of five minutes, 3.6grams (0.36 moles) of concentrated hydrochloric acid is added to thereaction mass. The reaction mass is then aged at -10° C. for a period of20 minutes. At the end of the 20 minute period the reaction mass isneutralized with solid anhydrous sodium acetate.

4.0 Grams of anhydrous citric acid followed by rapid addition of 870grams of allyl alcohol (15.0 moles) is added to the reaction mass. Thereaction mass is warmed to 25° C. The reaction mass is then heatedgradually to 150° C. at atmospheric pressure. During this period,methylformate, methanol and allyl alcohol are distilled through thebidwell trap at, respectively, 55°-64° C., 64°-90° C. and 90°-150° C.After 7 hours the reaction mass reaches 150° C. The reaction mass isthen stirred at 150° C. for a period of 2 hours. At the end of the 2hour period, the reaction mass is cooled to 25° C. and washed with 1liter of saturated sodium chloride solution. The washed crude reactionmass weighing 1825 grams is charged to a 3 liter still yielding thefollowing fractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         30-110      100-140  2.3                                            2         116         144      2.3                                            3         122         145      2.3                                            4         128         148      2.3                                            5         128         220      2.3                                            ______________________________________                                    

Fractions 2-5 from the first distillation is then distilled on an 18"×2"Goodloe column yielding the following fractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         80/83       138/138  2/1                                            2          92         138      3.0                                            3          87         138      1.0                                            4          90         140      1.0                                            5         100         140      1.0                                            6         109         144      1.0                                            7         109         145      1.0                                            8         109         148      1.0                                            9         109         149      1.0                                            10        109         149      1.0                                            11        111         149      1.0                                            12        111         150      1.0                                            13        111         150      1.0                                            14        111         180      1.0                                            15        111         200      1.0                                            16        110         220      1.0                                            ______________________________________                                    

Fractions 1-3 contain recovered alpha ionone. Fractions 7-15 are bulkedand contain the isomers having the structures: ##STR168## with the moleratio of compound having the structure: ##STR169## compounds having thestructures: ##STR170## being about 48:1. This represents an exception tothe rule that the branched rather than the straight chain material isproduced via Claisen rearrangement using a citric acid catalyst.

The resulting product has a sweet, floral, fruity, bark-like and greenaroma profile.

FIG. 15 is the GLC profile for the crude reaction product prior todistillation (Conditions: SE-30 column programmed at 100°-220° C. at 8°C. per minute).

FIG. 16 is the GLC profile for bulked fractions 7-15 of the seconddistillation (Conditions: SE-30 column programmed at 100°-220° C. at 8°C. per minute).

EXAMPLE X(B) PREPARATION OF ALLYL BETA IONONE ISOMER mixture Reactions##STR171##

Into a 3 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and cooling coils is placed 650 grams of beta ionone(3.4 moles); 700 ml. anhydrous methanol; and 394 grams (3.7 moles) oftrimethylorthoformate. With stirring, the reaction mass is cooled to-10° C. Over a period of 30 minutes while maintaining the reaction massat -10° C, 3 grams of concentrated hydrochloric acid is added to thereaction mass. After the addition of hydrochloric acid, at -10° C. overa period of 15 minutes, 3 grams of sodium acetate is added. After theaddition of the sodium acetate, over a period of 15 minutes, 470 ml. ofallyl alcohol and 3.3 grams of citric acid is added to the reactionmass. The reaction mass is then heated and methylformate, methanol andallyl alcohol is removed via a bidwell trap. The reaction mass ismaintained at 58° C. for a period of 4.5 hours while removing theabove-mentioned products. The reaction mass is then heated to 140°-150°C. and maintained at 140°-150° C. with stirring for a period of 4 hours.At the end of the 4 hour period, the reaction mass is cooled to roomtemperature and is washed with one 500 ml. portion of saturated sodiumchloride solution.

The reaction mass is then distilled on a 2" splash column yielding thefollowing fractions:

    ______________________________________                                                  VAPOR       LIQUID   VACUUM                                         FRACTION  TEMP.       TEMP.    mm/Hg.                                         NO.       (°C.)                                                                              (°C.)                                                                           PRESSURE                                       ______________________________________                                        1         84/105      110/118  2.8/2.5                                        2         105         127      2.5                                            3         120         140      2.5                                            4         128         200      2.5                                            ______________________________________                                    

Fractions 2-4 are bulked and redistilled on a 1' Goodloe column yieldingthe following fractions:

    ______________________________________                                                 VAPOR    LIQUID    VACUUM                                            FRACTION TEMP.    TEMP.     mm/Hg.   REFLUX                                   NO.      (°C.)                                                                           (°C.)                                                                            PRESSURE RATIO                                    ______________________________________                                        1         90      128       2.0       4:1                                     2        105      137       2.0       4:1                                     3        109      140       2.0       4:1                                     4        109      140       2.0       4:1                                     5        109      140       2.0       9:1                                     6        109      140       2.5      19:1                                     7        112      141       2.0      19:1                                     8        113      142       2.0      19:1                                     9        113      143       2.0      19:1                                     10       113      143       2.0      19:1                                     11       113      144       2.0      19:1                                     12       113      145       2.0      19:1                                     13       113      145       2.0      19:1                                     14       118      155       2.0      19:1                                     15       118      147       2.0      19:1                                     16       120      147       2.0      19:1                                     17       121      147       2.0      19:1                                     18       126      150       2.0      19:1                                     19       128      158       2.0      19:1                                     20       132      195       2.0      19:1                                     21       125      220       2.0      19:1                                     ______________________________________                                    

FIG. 17 is the GLC profile for the crude reaction product prior todistillation on a 2" splash column, containing the compounds having thestructures: ##STR172##

FIG. 18 is the GLC profile for fraction 14 of the foregoing seconddistillation on the 1' Goodloe column containing the compounds havingthe structures: ##STR173##

The resulting mixture has a floral, fruity and green aroma profile.

EXAMPLE XI SPICY-FLORAL FRAGRANCES

The following spicy-floral fragrances are prepared:

    ______________________________________                                                     PARTS BY WEIGHT                                                                 XI     XI     XI   XI   XI   XI                                INGREDIENTS    (A)    (B)    (C)  (D)  (E)  (F)                               ______________________________________                                        Coumarin       6.0    6.0    6.0  6.0  6.0  6.0                               Musk Ambrette  8.0    8.0    8.0  8.0  8.0  8.0                               Benzyl Salicylate                                                                            12.0   12.0   12.0 12.0 12.0 12.0                              Bergamot Oil   6.0    6.0    6.0  6.0  6.0  6.0                               Hydroxycitronellal                                                                           5.0    5.0    5.0  5.0  5.0  5.0                               Lavender Oil   4.0    4.0    4.0  4.0  4.0  4.0                               Patchouli Oil Light                                                                          1.0    1.0    1.0  1.0  1.0  1.0                               Phenyl Ethyl Alcohol                                                                         6.0    6.0    6.0  6.0  6.0  6.0                               Gamma Methyl Ionone                                                                          1.0    1.0    1.0  1.0  1.0  1.0                               Vetivert Oil   8.0    8.0    8.0  8.0  8.0  8.0                               Benzyl Acetate 14.0   14.0   14.0 14.0 14.0 14.0                              Linalool       8.0    8.0    8.0  8.0  8.0  8.0                               Amyl Cinnamic  10.0   10.0   10.0 10.0 10.0 10.0                              Aldehyde                                                                      Indole (10% in diethyl                                                                       1.0    1.0    1.0  1.0  1.0  1.0                               phthalate)                                                                    Eugenol        2.0    2.0    2.0  2.0  2.0  2.0                               Mixture of compounds                                                                         8.0    0.0    0.0  0.0  0.0  0.0                               having the structures:                                                         ##STR174##                                                                   and                                                                            ##STR175##                                                                   produced according to                                                         Example III (mole ratio                                                       of compound having the                                                        structure:                                                                     ##STR176##                                                                   to compound having the structure:                                              ##STR177##                                                                   = 20:1)                                                                       Mixture of compounds                                                                         0.0    8.0    0.0  0.0  0.0  0.0                               having the structures:                                                         ##STR178##                                                                   and                                                                            ##STR179##                                                                   with the mole ratio of                                                        compound having the                                                           structure:                                                                     ##STR180##                                                                   to the compound having                                                        the structure:                                                                 ##STR181##                                                                   being 1:4                                                                     The dimethyl ketal of                                                                        0.0    0.0    8.0  0.0  0.0  0.0                               1-acetyl-3,3-dimethyl                                                         cyclohexane produced                                                          according to Example I                                                        Mixture of compounds                                                                         0.0    0.0    0.0  8.0  0.0  0.0                               having the structures:                                                         ##STR182##                                                                   and                                                                            ##STR183##                                                                   with the mole ratio of                                                        compound having the                                                           structure:                                                                     ##STR184##                                                                   to the compound having                                                        the structure:                                                                 ##STR185##                                                                   being 4:1.                                                                    Mixture of compounds                                                                         0.0    0.0    0.0  0.0  8.0  0.0                               having the structures:                                                         ##STR186##                                                                   and                                                                            ##STR187##                                                                   with the mole ratio of                                                        compound having the                                                           structure:                                                                     ##STR188##                                                                   to the compound having                                                        the structure:                                                                 ##STR189##                                                                   being 4:1.                                                                    Mixture of compounds                                                                         0.0    0.0    0.0  0.0  0.0  8.0                               having the structures:                                                         ##STR190##                                                                    ##STR191##                                                                   and                                                                            ##STR192##                                                                   produced according to                                                         Example X (A) with the                                                        mole ratio of compound                                                        having the structure:                                                          ##STR193##                                                                   to the compounds having                                                       the structures:                                                                ##STR194##                                                                   and                                                                            ##STR195##                                                                   being 46:1.                                                                   ______________________________________                                    

The perfume formulations can be described as follows:

Example XI(A): Spicy and floral with galbanum-like, green herbaceous andchypre undertones.

Example XI(B): Spicy and floral with woody, pine and floral undertonesand citrusy and lemony topnotes.

Example XI(C): Spicy and floral with a pear undertone and green,cedarwood and minty topnotes.

Example XI(D): Spicy and floral with sweet, fruity, raspberry, jasmin,floral and rosey undertones and jasmin topnotes.

Example XI(E): Spicy and floral with licorice, aniseed undertones andfruity, pineapple, green, woody, herbaceous, minty and camphoraceoustopnotes.

Example XI(F): Spicy and floral aroma with sweet, floral, fruity,bark-like and green undertones.

EXAMPLE XII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of a perfume substance as set forth inTable III below. The resulting powder has an excellent aroma as setforth in Table III below:

                  TABLE III                                                       ______________________________________                                        PERFUME SUBSTANCE  AROMA DESCRIPTION                                          ______________________________________                                        Mixture of compounds having the                                                                  A galbanum-like,                                           the structure:     floral, green,                                              ##STR196##        herbaceous and chypre aroma profile.                       and                                                                            ##STR197##                                                                   prepared according to Example III                                             with the mole ratio of compound                                               having the structure:                                                          ##STR198##                                                                   to the compound having the                                                    structure:                                                                     ##STR199##                                                                   being 20:1                                                                    Mixture of compounds having the                                                                  A woody, piney,                                            structures:        floral aroma                                                ##STR200##        with citrusy lemony topnotes.                              and                                                                            ##STR201##                                                                   with the mole ratio of compound                                               having the structure:                                                          ##STR202##                                                                   to the compound having the                                                    structure:                                                                     ##STR203##                                                                   being 4:1.                                                                    Compound having the structure:                                                                   A sweet, pear, fruity aroma                                 ##STR204##        with green, cedarwood and minty topnotes.                  prepared according to Example I.                                              Mixture of compounds having the                                                                  A sweet, fruity,                                           structures:        raspberry-like,                                             ##STR205##        jasmin, floral and rosey aroma with jasmin topnotes.       and                                                                            ##STR206##                                                                   with the mole ratio of compound                                               having the structure:                                                          ##STR207##                                                                   to the compound having the                                                    structure:                                                                     ##STR208##                                                                   being 4:1.                                                                    Mixture of compounds having the                                                                  A licorice and aniseed                                     structures:        aroma with fruity, pineapple,                               ##STR209##        green, woody, herbaceous, minty and camphoraceous                             topnotes.                                                  and                                                                            ##STR210##                                                                   with the mole ratio of compound                                               having the structure:                                                          ##STR211##                                                                   to the compound having the                                                    structure:                                                                     ##STR212##                                                                   being 4:1                                                                     Mixture of compounds having the                                                                  A sweet, floral, fruity,                                   structures:        bark-like and green                                         ##STR213##        aroma profile.                                              ##STR214##                                                                   and                                                                            ##STR215##                                                                   with the mole ratio of compound                                               having the structure:                                                          ##STR216##                                                                   to the compounds having the                                                   structures:                                                                    ##STR217##                                                                   and                                                                            ##STR218##                                                                   being 46:1.                                                                   Perfume composition of                                                                           Spicy and floral with                                      Example XI(A)      galbanum-like, green,                                                         herbaceous and chypre                                                         undertones.                                                Perfume composition of                                                                           Spicy and floral with woody,                               Example XI(B)      pine and floral undertones                                                    and citrusy and lemony                                                        topnotes.                                                  Perfume composition of                                                                           Spicy and floral with a                                    Example XI(C)      pear undertone and green,                                                     cedarwood and minty top-                                                      notes.                                                     Perfume composition of                                                                           Spicy and floral with                                      Example XI(D)      sweet, fruity, raspberry,                                                     jasmin, floral and rosey                                                      undertones and jasmin top-                                                    notes.                                                     Perfume composition of                                                                           Spicy and floral with                                      Example XI(E)      licorice, aniseed under-                                                      tones and fruity, pine-                                                       apple, green, woody,                                                          herbaceous, minty and                                                         camphoraceous topnotes.                                    Perfume composition of                                                                           Spicy and floral aroma                                     Example XI(F)      with sweet, floral, fruity,                                                   bark-like and green under-                                                    tones.                                                     ______________________________________                                    

EXAMPLE XIII PERFUME LIQUID DETERGENT

Concentrated liquid detergent (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976, the specification for which is incorporated herein byreference) with aroma nuances as set forth in Table III of Example XII,supra, are prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and0.35% of the substances as set forth in Table III of Example XII, supra.They are prepared by adding and homogeneously mixing the appropriatequantity of fragrance formulation of Table III of Example XII, supra, inthe liquid detergents. The detergents all possess excellent aromas, theintensity increasing with greater concentration of perfume substance ofTable III of Example XII.

EXAMPLE XIV PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The perfume substances as set forth in Table III of Example XII, supra,are incorporated into colognes at concentrations of 2.0%, 2.5%, 3.0%,3.5%, 4.0%, 4.5% and 5.0% in 75%, 80%, 85% and 90% aqueous food gradeethanol; and into handkerchief perfumes at concentrations of 15%, 20%,25%, and 30% (in 80%, 85%, 90% and 95% aqueous food grade ethanolsolutions). Distinctive and definitive aroma nuances as set forth inTable III of Example XII are imparted to the colognes and to thehanderchief perfumes at all levels indicated above.

EXAMPLE XV PREPARATION OF SOAP COMPOSITIONS

One hundred grams of soap chips (IVORY®, produced by the Procter &Gamble Company of Cincinnati, Ohio are mixed with 1 gram of each of theperfumery substances of Table III of Example XII, supra, untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 3 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, on cooling, manifest excellentaromas as set forth in Table III of Example XII, supra.

EXAMPLE XVI PREPARATION OF SOLID DETERGENT COMPOSITIONS

A detergent is prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948, (the specification for whichis incorporated herein by reference):

    ______________________________________                                        Ingredient              Percent by Weight                                     ______________________________________                                        Neodol ® 45-11 (a C.sub.14 -C.sub.15 alcohol ethoxy-                                              12                                                    lated with 11 moles of ethylene oxide)                                        Sodium carbonate        55                                                    Sodium citrate          20                                                    Sodium sulfate, water brighteners                                                                     q.s.                                                  ______________________________________                                    

This detergent is phosphate-free detergent. A total of 100 grams of saiddetergent is admixed with 0.10, 0.15, 0.20 and 0.25 grams of thesubstances of Table III of Example XII, supra. The detergent samples ineach case have excellent aromas as set forth in Table III of ExampleXII, supra.

EXAMPLE XVII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396, (the disclosure of which is incorporated by reference herein)a nonwoven cloth substrate useful as a drier-added fabric softeningarticle of manufacture is prepared wherein the substrate, the substratecoating and the outer coating and the perfuming material are as follows:

1. A water dissolvable paper ("Dissolvo Paper");

2. Adogen 448 (melting point about 140° F.) as the substrate coating;and

3. An outer coating having the following formulation (melting pointabout 150° F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1 of one of the perfume substances of Table III of Example XII, supra.

Fabric softening compositions having aromas as set forth in Table III ofExample XII are prepared which essentially consist of a substrate havinga weight of about 3 grams per 100 square inches; a substrate coatinghaving a weight of about 1.85 grams per 100 grams of substrate; and anouter coating having a weight of about 1.4 grams per 100 square inchesof substrate, thereby providing a total aromatized substrate and outercoating weight ratio of about 1:1 by weight of the substrate. The aromasas set forth in Table III of Example XII are imparted in a pleasantmanner to the head space in the drier on operation thereof using each ofthe drier-added fabric softening nonwoven fabric samples.

In the following examples, Aromox® DMC-W and Aromox® DMMC-W are 30%aqueous solutions of dimethyl cocoamine oxide; and Aromox® NCMDW is a40% aqueous solution of N-cocomorpholine oxide produced by ArmacDivision of ADZO of Chicago, Ill.

EXAMPLE XVIII

Four drops of one or more of the perfume substances as set forth inTable III of Example XII, supra, is added to 2 grams of Aromox® DMC-W toproduce a clear premix. The clear premix is added to 200 grams ofCLOROX® with stirring resulting in a clear, stable, single phasesolution. Sufficient 1M aqueous NaOH is added to bring the pH of themixture up to 12.8. The solution remains substantially stable at 120° F.for a period of 7 days. When the 5% aqueous sodium hypochlorite solutionis used as a laundry bleach, the resulting laundry on dry-out in anatmosphere of 65% relative humidity yields substantially nocharacteristic "hypochlorite" odor but does have a faint, pleasant aromaas set forth in Table III of Example XII, supra. Furthermore, no suchcharacteristic "hypochlorite" aroma is retained on the hands of theindividual handling such laundry in both the wet and the dry states.

EXAMPLE XIX

Aromox® DMMC-W in various quantities is mixed with 0.1 grams of each ofthe substances of Table III of Example XII, supra. The resultingpremixes are then added to 200 grams of an aqueous 5% sodiumhypochlorite solution. Sufficient 12.5M aqueous NaOH is added to bringthe pH of each of the mixtures up to 13. The following results areobtained:

    ______________________________________                                        Percentage Aromox ®                                                                     Clarity of hypochlorite solution                                DMMC-W        after addition of premix                                        ______________________________________                                        0.23%         Clear after three days                                          0.15%         Clear after three days                                          0.08%         Initially slightly turbid; two phases exist                                   after three days                                                ______________________________________                                    

When the 5% aqueous sodium hypochlorite solutions are used as laundrybleaches, the resulting laundry batches on dry-out in an atmosphere of65% relative humidity yields substantially no characteristic"hypochlorite" odor but do have faint, pleasant aromas as set forth inTable III of Example XII, supra. Furthermore, no such characteristic"hypochlorite" aroma is retained on the hands of the individual handlingsuch laundry batches in both the wet and dry states.

EXAMPLE XX

Two grams of Aromox® DMMC-W are admixed with eight drops of each of theperfume substances of Table III of Example XII, supra. Each of thepremixes is then added with stirring to 200 grams of a 7% aqueoussolution of lithium hypochlorite. Sufficient 3M aqueous LiOH is added tobring the pH of the solution to 13.4. The mixtures are then heated to120° F. and maintained at that temperature with stirring for a period ofone week. The resulting solution remains clear in a single phase. Whenused as laundry bleaches, the resulting bleached laundry batches ondry-out in an atmosphere of 50% relative humidity retain an aroma asdescribed in Table III of Example XII whereas without the use of thesubstances of Table III of Example XII, the bleached laundry batcheshave faint characteristic disagreeable "hypochlorite" aromas.

EXAMPLE XXI

Two grams of Aromox® DMMC-W are admixed with eight drops of each of thesubstances of Table III of Example XII, supra. The premixes are thenadded with stirring to 200 grams of a mixture containing 4.5% aqueoussodium hypochlorite and 4.5% aqueous lithium hypochlorite. Sufficient 4Maqueous LiOH is added to bring the pH of the solutions to 13.4. Themixtures are then heated to 120° F. and maintained at that temperaturefor a period of one week. The resulting solutions remain clear in asingle phase. When used as laundry bleach, the resulting bleachedlaundry batches on dry-out in an atmosphere of 50% relative humidityretain an aroma as set forth in Table III of Example XII, supra, whereaswithout the use of the perfume substances as set forth in Table III ofExample XII, supra, the bleached laundry batches have faintcharacteristic and disagreeable "hypochlorite" aromas.

EXAMPLE XXII

Two grams of Aromox® DMMC-W are admixed with eight drops of one of theperfume substances of Table III of Example XII, supra. These premixesare then added with stirring to 200 grams of mixture containing 4%aqueous sodium hypochlorite and 4% aqueous lithium hypochlorite.Sufficient 2M aqueous NaOH is added to bring the pH of the solutions to13.4. The mixtures are then heated to 110° F. and maintained at thattemperature with stirring for a period of two weeks. The resultingsolutions remain clear as a single phase when used as laundry bleaches.The resulting bleached laundry batches on dry-out in an atmosphere of50% relative humidity retain aromas as set forth in Table III of ExampleXII, supra whereas without the use of the perfume substances of TableIII of Example XII, supra, the bleached laundry batches have faint,characteristic disagreeable "hypochlorite" aromas.

EXAMPLE XXIII

Four drops of each of the substances of Table III of Example XIII,supra, are added to 1.5 grams of Aromox® NCMDW to produce a clearpremix. The clear premixes are added to 200 grams in each case ofCLOROX® with stirring resulting in a clear single phase solution.Sufficient 1M aqueous NaOH is added to bring the pH of the mixture up to12.8. The solution remains substantially stable at 120° F. for a periodof 7 days. When the 5% aqueous sodium hypochlorite solution is used as alaundry bleach, the resulting laundry on dry-out in an atmosphere of 65%relative humidity yields substantially no characteristic hypochloritearoma but does have a faint pleasant aroma as set forth in Table III ofExample XII, supra. Furthermore, no such characteristic "hypochlorite"aroma is retained on the hands of the individual handling such laundryin both the wet and the dry states.

EXAMPLE XXIV

Four drops of each of the substances of Table III of Example XII, supra,are added to 1 gram of n-undecyl dimethyl amine oxide to produce a clearpremix in each case. The clear premix is added to 200 grams of CLOROX®with stirring resulting in a clear, single phase solution. Sufficient 1Maqueous NaOH is added to bring the pH of the mixture to 12.8. Thesolution remains substantially stable at 120° F. for a period of 7 days.When the 5% aqueous sodium hypochlorite solution is used as a laundrybleach, the resulting laundry on dry-out in an atmosphere of 65%relative humidity yields substantially no characteristic hypochloriteodor but does have a faint pleasant odor as set forth in Table III ofExample XII, supra. Furthermore, no such characteristic "hypochlorite"odor is retained on the hands of the individual handling such laundry inboth the wet and the dry states.

EXAMPLE XXV

Four drops of each of the substances of Table III of Example XII, supra,is added to 1 gram of n-dodecyl dimethyl amine oxide to produce a clearpremix. The clear premix is added to 200 grams of CLOROX® with stirringresulting in a clear stable single phase solution. Sufficient 1M aqueousNaOH is added to bring the pH of the mixture up to 12.8. The solutionremains substantially stable at 120° F. for a period of 7 days. When the5% aqueous sodium hypochlorite solution is used as a laundry bleach, theresulting laundry on dry-out in an atmosphere of 65% relative humidityyields substantially no characteristic "hypochlorite" odor but does havea faint pleasant aroma as set forth in Table III of Example XII, supra.Furthermore, no such characteristic "hypochlorite" aroma is retained onthe hands of the individual handling such laundry in both the wet andthe dry states.

EXAMPLE XXVI

One gram of n-tridecyl dimethyl amine oxide is admixed with eight dropsof each of the substances of Table III of Example XII, supra. Each ofthe premixes is then, with stirring, added to 200 grams of a 7% aqueoussolution of lithium hypochlorite. Sufficient 3M aqueous LiOH is added tobring the pH of the solution to 13.4. The mixture is then heated to 120°F. and maintained at that temperature with stirring for a period of oneweek. The resulting solution remains clear in a single phase. When usedas a laundry bleach, the resulting bleached laundry on dryout in anatmosphere of 50% relative humidity retains an aroma as set forth inTable III of Example XII, supra; whereas without the use of any of thesubstances of Table III of Example XII, supra, the bleached laundry hasfaint, chrarcteristic, disagreeable "hypochlorite" aroma.

What is claimed is:
 1. A ketone-containing product prepared according tothe process comprising the steps of (1) reacting at a temperature in therange of from about -10° C. up to about 50° C. trimethyl orthoformatewith β-ionone according to the reaction: ##STR219## to form aketal-containing composition with the mole ratio of β-ionone:trimethylorthoformate being from about 1:1 to about 1:2; (ii) then reacting theketal-containing composition with allyl alcohol at a temperature in therange of from about 120° C. up to about 220° C. according to thereaction: ##STR220## in order to form a diallyl ketal with the moleratio of ketal-containing composition:allyl alcohol varying from about1:1 up to about 1:3; then rearranging the resulting diallyl ketal at atemperature of from about 120° C. up to about 220° C. according to thereaction: ##STR221## at a pH of between 2 and 6.5 in the presence of acitric acid catalyst and then fractionally distilling the resultingproduct at a vapor temperature of 105°-128° C. at 2.5 mm/Hg pressure. 2.A process for augmenting or enhancing the aroma of a consumable materialselected from the group consisting of perfume compositions, perfumedarticles and colognes comprising the step of adding to said consumablematerial an aroma augmenting or enhancing quantity of the productdefined according to claim
 1. 3. The product of claim 1 wherein in theprocess, the rearrangement reaction: ##STR222## is carried out at 150°C.
 4. A process for augmenting or enhancing the aroma of a consumablematerial selected from the group consisting of perfume compositions,perfumed articles and colognes comprising the step of adding to saidconsumable material, an aroma augmenting or enhancing quanitity of theproduct defined according to claim 3.